CN116234867A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN116234867A
CN116234867A CN202180063312.5A CN202180063312A CN116234867A CN 116234867 A CN116234867 A CN 116234867A CN 202180063312 A CN202180063312 A CN 202180063312A CN 116234867 A CN116234867 A CN 116234867A
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Prior art keywords
carbon atoms
formula
group
ring
chain hydrocarbon
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Inventor
赤坂哲郎
松山绫花
青木拓磨
河西裕
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/23—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/549—Silicon-containing compounds containing silicon in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/1462—Coatings
    • H01L27/14621—Colour filter arrangements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G02B3/0037—Arrays characterized by the distribution or form of lenses
    • G02B3/0056—Arrays characterized by the distribution or form of lenses arranged along two different directions in a plane, e.g. honeycomb arrangement of lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays

Abstract

The invention aims to provide a resin composition capable of improving at least one of heat resistance and visible light transmittance. The resin composition according to one embodiment of the present invention contains a colorant and a resin, and the colorant contains a compound represented by formula (I), formula (II), formula (III), or formula (IV).

Description

Resin composition
Technical Field
The invention relates to a resin composition, an optical filter and a solid-state imaging element.
Background
Optical filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma display devices, and solid-state imaging devices such as CCDs and CMOS sensors are manufactured from curable resin compositions. As the curable resin composition, a composition containing a phthalocyanine compound as a colorant is known (patent document 1). Patent document 1 describes that the composition can absorb near infrared rays to form a fine pattern.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2010-160380
Disclosure of Invention
However, the heat resistance of the curable resin composition of patent document 1 is insufficient, and when the resin composition is treated at a high temperature (for example, 120 ℃ or higher) for a predetermined time, the absorptivity of near infrared rays (700 nm to 3 μm) may be lowered. In addition, the transmittance of visible light of the resin composition is not sufficiently high. Accordingly, an object of the present invention is to provide a resin composition capable of improving at least one of heat resistance and visible light transmittance, preferably both heat resistance and visible light transmittance.
The resin composition according to one embodiment of the present invention contains a colorant and a resin, and the colorant contains a compound represented by formula (I), formula (II), formula (III), or formula (IV).
Figure BDA0004126813250000021
[ in the formula (I) and the formula (II),
R x1 ～R x4 each independently represents a chain hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,
the chain hydrocarbon group containing-CH 2 May be substituted by-O-,
the hydrogen atom contained in the chain hydrocarbon group may be substituted with a halogen atom,
the hydrogen atoms contained in the aryl and heteroaryl groups may each be independently substituted with a halogen atom, -OR 1 、－SR 1 or-NR 2 R 3 ，
R 1 Represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, wherein the chain hydrocarbon group contains-CH 2 Can be substituted by-O-, -NR 2 -or-N + (R 2 R 3 )X － Hydrogen atoms contained in the aryl group and the heteroaryl group may be each independently substituted with a halogen atom or a linear or branched alkoxy group having 1 to 20 carbon atoms,
R 2 and R is 3 Each independently represents a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms, and the-CH contained in the hydrocarbon group 2 May be substituted with-O-, or
R 2 And R is R 3 Are bonded to each other to form a ring,
x represents halogen atom, PF 6 、ClO 4 Or BF 4 ，
R in formula (I) y1 ～R y4 Each independently represents a chain hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,
the chain hydrocarbon group containing-CH 2 May be substituted by-O-,
the hydrogen atom contained in the chain hydrocarbon group may be substituted with a halogen atom,
the hydrogen atoms contained in the aryl and heteroaryl groups may each be independently substituted with a halogen atom, -OR 1 、－SR 1 or-NR 2 R 3 ，
Ring Z in formula (II) 1 And ring Z 2 Each independently represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms or a heteroaromatic ring having 2 to 20 carbon atoms,
the hydrogen atoms contained in the aromatic hydrocarbon ring and the heteroaromatic ring may be substituted with halogen atoms, chain hydrocarbon groups having 1 to 20 carbon atoms, -OR 1 、－SR 1 or-NR 2 R 3 ，
R 1 、R 2 Or R is 3 Where there are plural, they may be the same or different,
M 2 represents a divalent metal atom.]
Figure BDA0004126813250000031
[ in the formula (III) and the formula (IV),
R 1a ～R 1d 、R 2a ～R 2d 、R 3a ～R 3d and R is 4a ～R 4d Each independently represents a hydrogen atom, a halogen atom, a chain hydrocarbon group having 1 to 20 carbon atoms, -OR 1 、－SR 1 or-NR 2 R 3 ，R 1a ～R 1d 、R 2a ～R 2d 、R 3a ～R 3d And R is 4a ～R 4d At least one of them represents-SR 1 ，
R 1 Represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, wherein the chain hydrocarbon group contains-CH 2 Can be substituted by-O-, -NR 2 -or-N + (R 2 R 3 )X － Hydrogen atoms contained in the aryl group and the heteroaryl group may be each independently substituted with a halogen atom or a linear or branched alkoxy group having 1 to 20 carbon atoms,
R 2 and R is 3 Each independently represents a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms, and the-CH contained in the hydrocarbon group 2 May be substituted with-O-, or
R 2 And R is R 3 Are bonded to each other to form a ring,
x represents halogen atom, PF 6 、ClO 4 Or BF 4 ，
R A1 And R is A2 Each independently represents-OR 4 ，
R 4 Represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, wherein the chain hydrocarbon group contains-CH 2 Can be used asSubstituted by-O-, -NR 5 -or-N + (R 5 R 6 )X － －，
R 5 And R is 6 Each independently represents a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms,
R 1 、R 2 、R 3 、R 5 or R is 6 Where there are plural, they may be the same or different,
m in formula (III) 1 Represents a tetravalent metal atom or a nonmetallic atom,
m in formula (IV) 3 Represents a pentavalent metal atom or a non-metal atom,
y in formula (IV) － Representing a monovalent anion.]
The resin composition may further comprise a polymerizable compound and a polymerization initiator.
The resin may be a copolymer containing a structural unit derived from at least 1 selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond.
In the above formulas (I) to (IV),
R x1 ～R x4 can each independently represent an aryl group having 6 to 20 carbon atoms,
R y1 ～R y4 can each independently represent an aryl group having 6 to 20 carbon atoms,
ring Z 1 And ring Z 2 Can each independently represent an aromatic hydrocarbon ring having 6 to 20 carbon atoms,
M 2 it may be represented by Ru, fe, cu, zn, co, ni or Pd,
R 1a ～R 1d 、R 2a ～R 2d 、R 3a ～R 3d and R is 4a ～R 4d Can each independently represent a hydrogen atom or-SR 1 ，
R 4 Can represent a hydrogen atom or a C1-10 chain hydrocarbon group, and the chain hydrocarbon group contains-CH 2 Can be substituted by-O-, -NR 5 -or-N + (R 5 R 6 )X － －，
M 1 It is possible to represent Si which is,
M 3 p may be represented.
Here the number of the elements is the number,
R x1 ～R x4 can each independently represent an aryl group having 6 to 10 carbon atoms,
R y1 ～R y4 can each independently represent an aryl group having 6 to 10 carbon atoms,
ring Z 1 And ring Z 2 Can each independently represent an aromatic hydrocarbon ring having 6 to 10 carbon atoms,
M 2 it is possible to represent the value of Ru,
R 1 can represent an aryl group having 6 to 10 carbon atoms,
R 4 can represent a hydrogen atom or a C1-10 chain hydrocarbon group, and the chain hydrocarbon group contains-CH 2 Can be substituted by-O-or-N + (R 5 R 6 )X － －。
In addition, the colorant may contain a compound represented by formula (I) or formula (II).
The colorant may comprise a compound represented by any one of the following formulas.
Figure BDA0004126813250000051
[ formula, R A1 And R is A2 Representation of-OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 3 、－OCH 2 CH 2 N + (CH 3 ) 3 I － Or hydroxyl.]
An optical filter according to an embodiment of the present invention includes a cured product of the above resin composition.
The solid-state imaging device according to one embodiment of the present invention includes the optical filter described above.
The resin composition according to one embodiment of the present invention is excellent in at least one of heat resistance and visible light transmittance. Therefore, according to the present invention, an optical filter having improved heat resistance and/or visible light transmittance can be obtained. The cured product of the resin composition according to one embodiment of the present invention is capable of transmitting visible light sufficiently and absorbing a specific wavelength in the near infrared region, and therefore can be used as a near infrared cut filter. The cured product of the resin composition according to one embodiment of the present invention can be used as a near infrared ray transmission filter having a specific wavelength transmitting in the near infrared ray region.
Drawings
Fig. 1 is a schematic diagram showing one embodiment of a solid-state imaging element.
Detailed Description
In the present specification, me, ph, ts, and Pc represent methyl, phenyl, p-toluenesulfonyl, and phthalocyanine, respectively.
< resin composition >
The resin composition according to one embodiment of the present invention contains a colorant and a resin (hereinafter, referred to as a colorant (a) and a resin (B), respectively). The resin composition may further contain 1 or more of a polymerizable compound, a polymerization initiator, a solvent, and a leveling agent (hereinafter, sometimes referred to as a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and a leveling agent (F), respectively). In the present specification, the compounds exemplified as the respective components may be used alone or in combination of a plurality of compounds unless otherwise specified. The resin composition is preferably excellent in both heat resistance and visible light transmittance, and more preferably also excellent in light resistance.
< colorant (A) >
In the present specification, the colorant means a substance that absorbs a specific wavelength, and the range of the colorant includes, for example, a visible light absorber, an infrared absorber, a near infrared absorber, and an ultraviolet absorber. The colorant (a) includes a compound represented by formula (I), formula (II), formula (III) or formula (IV) (hereinafter, may be referred to as a colorant (A1)).
The compound represented by the formula (I) and the compound represented by the formula (II) are as follows.
Figure BDA0004126813250000061
In the formula (I) and the formula (II), R x1 ～R x4 Each independently represents a chain hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms. R is R x1 ～R x4 Preferably represents an aryl group having 6 to 20 carbon atoms.
R x1 ～R x4 Of the chain hydrocarbon groups having 1 to 20 carbon atoms, at least 1-CH 2 -may be substituted with-O-, and more than 1 hydrogen atom may be substituted with a halogen atom. R is R x1 ～R x4 The chain hydrocarbon group having 1 to 20 carbon atoms represented by the formula may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, 2-ethylbutyl, 3-dimethylbutyl, 1, 3-tetramethylbutyl, 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, neopentyl, 1-dimethylpropyl, 2-methylpentyl, 3-ethylpentyl, 1, 3-dimethylbutyl, 2-propylpentyl, 1-ethyl-1, 2-dimethylpropyl, 1-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2-ethylhexyl, 1-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 3-ethylheptyl, 2-dimethylheptyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1-methyloctyl, 1-ethylheptyl, 1-propylhexyl, 1-butylpentyl, 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl or 1-butylhexyl.
R x1 ～R x4 The aryl group having 6 to 20 carbon atoms is preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms. In the aryl group, more than 1 hydrogen atom may be substituted by a halogen atom, -OR 1 、－SR 1 or-NR 2 R 3 。
R 1 Represents a hydrogen atom; more than 1-CH 2 Can be substituted by－O－、－NR 2 -, or-N + (R 2 R 3 )X － -a chain hydrocarbon group of 1 to 10 carbon atoms; aryl groups having 6 to 20 carbon atoms in which 1 or more hydrogen atoms may be substituted with a halogen atom or a linear or branched alkoxy group having 1 to 20 carbon atoms; or a heteroaryl group having 2 to 20 carbon atoms, wherein 1 or more hydrogen atoms may be substituted with a halogen atom or a linear or branched alkoxy group having 1 to 20 carbon atoms. R is R 1 Aryl having 6 to 20 carbon atoms is preferable, aryl having 6 to 18 carbon atoms is more preferable, aryl having 6 to 12 carbon atoms is more preferable, and aryl having 6 to 10 carbon atoms is particularly preferable. R is R 1 For example, phenyl, hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, phenyl, o-tolyl, m-tolyl, p-tolyl, 2, 4-xylyl, 2, 6-xylyl, 3, 5-xylyl, mesityl, 1-naphthyl, 2-naphthyl or 4-biphenyl may be mentioned. R is R 1 When there are plural, they may be the same or different.
R 2 And R is 3 Each independently represents a hydrogen atom; or more than 1-CH 2 -a chain hydrocarbon group of 1 to 10 carbon atoms which may be substituted with-O-. R is R 2 And R is 3 Can each be, independently of the other, for example, a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, 2-ethylbutyl, 3-dimethylbutyl, 1, 3-tetramethylbutyl, 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, neopentyl, 1-dimethylpropyl, 2-methylpentyl, 3-ethylpentyl, 1, 3-dimethylbutyl, 2-propylpentyl, 1-ethyl-1, 2-dimethylpropyl, 1-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2-ethylhexyl, 1-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 3-ethylheptyl, 2-dimethylheptyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1-methyloctyl, 1-ethylheptylCycloheptyl, 1-propylhexyl, 1-butylpentyl, 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl, or 1-butylhexyl. Alternatively, R 2 And R is R 3 Are bonded to each other to form a ring. From R 2 And R is 3 The ring to be formed may be, for example, a ring containing a nitrogen atom such as a pyrrolidine ring, a piperidine ring, or a morpholine ring. R is R 2 Or R is 3 When there are plural, they may be the same or different.
X is halogen atom, PF 6 、ClO 4 Or BF 4 。
R x1 ～R x4 Examples of the aryl group having 6 to 20 carbon atoms include phenyl, o-tolyl, m-tolyl, p-tolyl, 2, 4-xylyl, 2, 6-xylyl, 3, 5-xylyl, mesityl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2- (n-propyl) phenyl, 3- (n-propyl) phenyl, 4- (n-propyl) phenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 2- (n-butyl) phenyl, 3- (n-butyl) phenyl, 4- (n-butyl) phenyl, 2- (sec-butyl) phenyl, 3- (sec-butyl) phenyl, 4- (sec-butyl) phenyl, 2- (tert-butyl) phenyl, 3- (tert-butyl) phenyl, 4- (tert-butyl) phenyl 4- (n-pentyl) phenyl, 4- (n-hexyl) phenyl, 4- (n-heptyl) phenyl, 4- (2-ethylhexyl) phenyl, 4- (n-octyl) phenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, p-terphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 4-vinylphenyl, 3, 5-di (tert-butyl) phenyl, 3, 5-di (tert-butyl) -4-methylphenyl, 2, 6-bis (1-methylethyl) phenyl, 2,4, 6-tris (1-methylethyl) phenyl, 4-cyclohexylphenyl, 4- (1, 3-tetramethylbutyl) phenyl, 6-methyl-2-naphthyl, 5,6,7, 8-tetrahydro-1-naphthyl, 5,6,7, 8-tetrahydro-2-naphthyl, fluorenyl, phenanthryl, anthracenyl, 2-dodecylphenyl, 3-dodecylphenyl, 4-dodecylphenyl Phenanthryl, or fluorenyl. The aryl group is preferably phenyl, o-tolyl, m-tolyl, p-tolyl, 2, 4-xylyl, 2, 6-xylyl, 3, 5-xylyl, mesityl, 4- (t-butyl) phenyl, 2-methoxyphenyl, 3-methoxyphenyl or 4-methoxyphenyl, more preferably phenyl, o-tolyl, m-tolyl, p-tolyl, 4- (t-butyl) phenyl, 2-methoxyphenyl, 3-methoxyphenyl or 4-methoxyphenyl, still more preferably phenyl.
R x1 ～R x4 In the heteroaryl group having 2 to 20 carbon atoms, 1 OR more hydrogen atoms may be substituted with a halogen atom, -OR 1 、－SR 1 or-NR 2 R 3 。R 1 ～R 3 As defined above. R is R x1 ～R x4 The heteroaryl group having 2 to 20 carbon atoms represented by the formula (I) may be, for example, 2-pyrrolyl, 3-pyrrolyl, 2-furyl, 3-furyl, 2-thiophenyl, 3-thiophenyl, 1-imidazolyl, 2-imidazolyl, 1-methyl-2-imidazolyl 2-thiazolyl, 3-thiazolyl, 4-thiazolyl, 2-thiazolyl
Figure BDA0004126813250000091
Azolyl, 3->
Figure BDA0004126813250000092
Azolyl, 4->
Figure BDA0004126813250000093
Oxazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-pyrazinyl, 5-pyrimidinyl, 2-benzofuranyl, 3-benzofuranyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzo- >
Figure BDA0004126813250000094
Oxazolyl, 2-quinolinyl, 3-quinolinyl, 4-quinolinyl, 5-quinolinyl, 6-quinolinyl, 7-quinolinyl, 8-quinolinyl, 2-benzothienyl, 3-benzothienyl, indolyl, carbazolyl, or acridinyl.
In the formula (I), R y1 ～R y4 Each independently represents a chain hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms. R is R y1 ～R y4 Preferably represents an aryl group having 6 to 20 carbon atoms.
R y1 ～R y4 Of the chain hydrocarbon groups having 1 to 20 carbon atoms, at least 1-CH 2 -may be substituted with-O-, and more than 1 hydrogen atom may be substituted with a halogen atom. R is R y1 ～R y4 The chain hydrocarbon group having 1 to 20 carbon atoms represented by the formula may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, 2-ethylbutyl, 3-dimethylbutyl, 1, 3-tetramethylbutyl, 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, neopentyl, 1-dimethylpropyl, 2-methylpentyl, 3-ethylpentyl, 1, 3-dimethylbutyl, 2-propylpentyl, 1-ethyl-1, 2-dimethylpropyl, 1-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2-ethylhexyl, 1-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 3-ethylheptyl, 2-dimethylheptyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1-methyloctyl, 1-ethylheptyl, 1-propylhexyl, 1-butylpentyl, 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl or 1-butylhexyl.
R y1 ～R y4 The aryl group having 6 to 20 carbon atoms is preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms. In the aryl group, more than 1 hydrogen atom may be substituted by a halogen atom, -OR 1 、－SR 1 or-NR 2 R 3 。R 1 ～R 3 As defined above. R is R y1 ～R y4 The aryl group having 6 to 20 carbon atoms may be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, 2, 4-xylyl, 2, 6-xylyl, 3, 5-xylyl, mesityl, or 2-ethylPhenyl, 3-ethylphenyl, 4-ethylphenyl, 2- (n-propyl) phenyl, 3- (n-propyl) phenyl, 4- (n-propyl) phenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 2- (n-butyl) phenyl, 3- (n-butyl) phenyl, 4- (n-butyl) phenyl, 2- (sec-butyl) phenyl, 3- (sec-butyl) phenyl, 4- (sec-butyl) phenyl, 2- (tert-butyl) phenyl, 3- (tert-butyl) phenyl, 4- (n-pentyl) phenyl, 4- (n-hexyl) phenyl, 4- (n-heptyl) phenyl, 4- (2-ethylhexyl) phenyl, 4- (n-octyl) phenyl, 2-methoxyphenyl 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, p-terphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 4-vinylphenyl, 3, 5-di (tert-butyl) phenyl, 3, 5-di (tert-butyl) -4-methylphenyl, 2, 6-bis (1-methylethyl) phenyl, 2,4, 6-tris (1-methylethyl) phenyl, 4-cyclohexylphenyl, 4- (1, 3-tetramethylbutyl) phenyl, 6-methyl-2-naphthyl 5,6,7, 8-tetrahydro-1-naphthyl, 5,6,7, 8-tetrahydro-2-naphthyl, fluorenyl, phenanthryl, anthracyl, 2-dodecylphenyl, 3-dodecylphenyl, 4-dodecylphenyl, phenanthryl, or fluorenyl. The aryl group is preferably phenyl, o-tolyl, m-tolyl, p-tolyl, 2, 4-xylyl, 2, 6-xylyl, 3, 5-xylyl, mesityl, 4- (t-butyl) phenyl, 2-methoxyphenyl, 3-methoxyphenyl or 4-methoxyphenyl, more preferably phenyl or 4- (t-butyl) phenyl, further preferably 4- (t-butyl) phenyl.
R y1 ～R y4 In the heteroaryl group having 2 to 20 carbon atoms, 1 OR more hydrogen atoms may be substituted with a halogen atom, -OR 1 、－SR 1 or-NR 2 R 3 。R 1 ～R 3 As defined above. R is R y1 ～R y4 The heteroaryl group having 2 to 20 carbon atoms may be, for example, a 2-pyrrolyl group or a 3-pyrrolyl group-pyrrolyl, 2-furyl, 3-furyl, 2-thiophenyl, 3-thiophenyl, 1-imidazolyl, 2-imidazolyl, 1-methyl-2-imidazolyl 2-thiazolyl, 3-thiazolyl, 4-thiazolyl, 2-fluviuium
Figure BDA0004126813250000101
Azolyl, 3->
Figure BDA0004126813250000102
Azolyl, 4->
Figure BDA0004126813250000103
Oxazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidine, 2-pyrazinyl, 5-pyrimidine, 2-benzofuranyl, 3-benzofuranyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzo->
Figure BDA0004126813250000104
Oxazolyl, 2-quinolinyl, 3-quinolinyl, 4-quinolinyl, 5-quinolinyl, 6-quinolinyl, 7-quinolinyl, 8-quinolinyl, 2-benzothienyl, 3-benzothienyl, indolyl, carbazolyl or acridinyl.
In formula (II), ring Z 1 And ring Z 2 Each independently represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms or a heteroaromatic ring having 2 to 20 carbon atoms. Ring Z 1 And ring Z 2 Preferably, each independently represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms.
The aromatic hydrocarbon ring having 6 to 20 carbon atoms is preferably an aromatic hydrocarbon ring having 6 to 16 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms. In the aromatic hydrocarbon ring, 1 OR more hydrogen atoms may be substituted with a halogen atom, a chain hydrocarbon group having 1 to 20 carbon atoms, -OR 1 、－SR 1 or-NR 2 R 3 。R 1 ～R 3 As defined above. The aromatic hydrocarbon ring having 6 to 20 carbon atoms may be, for example, a benzene ring, a 2-methylbenzene ring, a 3-methylbenzene ring, a 2, 5-dimethylbenzene ring, a 3, 4-dimethylbenzene ring, a 2-ethylbenzene ring, or a 3-ethylbenzene ring2, 5-diethylbenzene ring, 3, 4-diethylbenzene ring, 2-isopropylbenzene ring, 3-isopropylbenzene ring, 2, 5-diisopropylbenzene ring, 3, 4-diisopropylbenzene ring, 2- (tert-butyl) benzene ring, 3- (tert-butyl) benzene ring, 2, 5-di (tert-butyl) benzene ring, 3, 4-di (tert-butyl) benzene ring, 2-phenylbenzene ring, 3-phenylbenzene ring, 2, 5-diphenylbenzene ring, 3, 4-diphenylbenzene ring, 2- (4-methylphenyl) benzene ring, 3- (4-methylphenyl) benzene ring, 2, 5-di (4-methylphenyl) benzene ring, 3, 4-di (4-methylphenyl) benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring or pyrene ring. The aromatic hydrocarbon ring is preferably a benzene ring, a 2-methylbenzene ring, a 3-methylbenzene ring, a 2, 5-dimethylbenzene ring, a 3, 4-dimethylbenzene ring, a 2, 5-diphenylbenzene ring, a 3, 4-diphenylbenzene ring or a naphthalene ring, more preferably a benzene ring, a 2, 5-dimethylbenzene ring, a 3, 4-dimethylbenzene ring, a 2, 5-diphenylbenzene ring or a 3, 4-diphenylbenzene ring, and still more preferably a benzene ring.
In the heteroaromatic ring with 2-20 carbon atoms, more than 1 hydrogen atom can be substituted into halogen atom, chain alkyl with 1-20 carbon atoms, -OR 1 、－SR 1 or-NR 2 R 3 。R 1 ～R 3 As defined above. The heteroaromatic ring having 2 to 20 carbon atoms may be, for example, furan ring, benzofuran ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, thiophene ring, benzothiophene ring, or the like,
Figure BDA0004126813250000111
Azole ring, benzo->
Figure BDA0004126813250000112
An azole ring, a thiazole ring, a benzothiazole ring, an indole ring, a carbazole ring, an acridine ring, an imidazole ring, a benzimidazole ring, a quinoline ring, or an isoquinoline ring.
In the formula (I) and the formula (II), M 2 Represents a divalent metal atom. From the viewpoint of obtaining excellent optical characteristics and from the viewpoint of easiness in obtaining raw materials, M 2 Preferably Ru, fe, cu, zn, co, ni or Pd, more preferably Ru.
As specific examples of the compound represented by the formula (I),the compounds represented by the following formula are exemplified. The compound represented by the following formula is a compound represented by the formula (I), and R x1 ～R x4 Is phenyl, R y1 ～R y4 Is 4- (tert-butyl) phenyl, M 2 Is Ru compound. The above-mentioned compounds have absorption maxima, for example, at 720 to 820nm or 760 to 780 nm.
Figure BDA0004126813250000113
Specific examples of the compound represented by the formula (II) include compounds represented by the following formulas. The compound represented by the following formula is a compound represented by the formula (II), and R x1 ～R x4 Is phenyl, Z 1 And ring Z 2 Is benzene ring, M 2 Is Ru compound. The compounds mentioned above may have an absorption maximum at, for example, 700 to 760nm or 700 to 720 nm.
Figure BDA0004126813250000121
The compound represented by the formula (III) and the compound represented by the formula (IV) are as follows.
Figure BDA0004126813250000122
In the formula (III) and the formula (IV), R 1a ～R 1d 、R 2a ～R 2d 、R 3a ～R 3d And R is 4a ～R 4d (hereinafter, they are sometimes collectively referred to as R 1a ～R 4d ) Each independently represents a hydrogen atom, a halogen atom, a chain hydrocarbon group having 1 to 20 carbon atoms, -OR 1 、－SR 1 or-NR 2 R 3 。R 1 ～R 3 As defined above.
R 1a ～R 4d The halogen atom represented may be, for example, fluorine, chlorine, bromine or iodine.
R 1a ～R 4d Chain of 1 to 20 carbon atomsThe hydrocarbon group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, 2-ethylbutyl, 3-dimethylbutyl, 1, 3-tetramethylbutyl, 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, neopentyl, 1-dimethylpropyl, 2-methylpentyl, 3-ethylpentyl, 1, 3-dimethylbutyl, 2-propylpentyl 1-ethyl-1, 2-dimethylpropyl, 1-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2-ethylhexyl, 1-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 3-ethylheptyl, 2-dimethylheptyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1-methyloctyl, 1-ethylheptyl, 1-propylhexyl, 1-butylpentyl, 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl or 1-butylhexyl.
R 1a ～R 4d At least one of them represents-SR 1 . Preferably R 1a 、R 1d 、R 2a 、R 2d 、R 3a 、R 3d 、R 4a And R is 4d representation-SR 1 ，R 1b 、R 1c 、R 2b 、R 2c 、R 3b 、R 3c 、R 4b And R is 4c Represents a hydrogen atom. Here, -SR 1 preferably-SPh.
In the formula (III) and the formula (IV), R A1 And R is A2 Each independently represents-OR 4 。R 4 Represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms. R is R 4 Preferably a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms.
R 4 Of the chain hydrocarbon groups having 1 to 10 carbon atoms, at least 1-CH 2 Can be substituted by-O-, -NR 5 -or-N + (R 5 R 6 )X － －。
R 5 And R is 6 Each independently represents a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms。R 5 And R is 6 For example, each independently may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl or n-octyl. R is R 5 Or R is 6 When there are plural, they may be the same or different.
R 4 Represented by more than 1-CH 2 Can be substituted by-O-, -NR 5 -or-N + (R 5 R 6 )X － The chain hydrocarbon group having 1 to 10 carbon atoms may be, for example, methyl group or-CH group 2 CH 2 OCH 3 、－CH 2 CH 2 OCH 2 CH 3 、－CH 2 CH 2 OCH 2 CH 2 OCH 3 、－CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 3 、－CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 3 OCH 3 、－CH 2 CH 2 N + (CH 3 ) 3 I － 、－CH 2 CH 2 N + (CH 3 ) 2 CH 2 CH 3 I － 、－CH 2 CH 2 N + (CH 2 CH 3 ) 3 I － or-CH 2 CH 2 OCH 2 CH 2 N + (CH 3 ) 3 I － 。
In the formula (III), M 1 Represents a tetravalent metal atom or a nonmetallic atom. M is M 1 For example, si, ge or Sn. From the viewpoint of obtaining excellent optical characteristics, M 1 Si is preferred. In the formula (IV), M 3 Representing a pentavalent metal atom or a non-metal atom. M is M 3 For example P, as or Sb. From the viewpoint of obtaining excellent optical characteristics, M 3 Preferably P.
In the formula (IV), Y － Representing a monovalent anion. Y is Y － There are no particular restrictions, and examples thereof include halide ions, hexafluorophosphate ions, perchlorate ions, tetrafluoroborate ions, benzenesulfonate ions and p-toluenesulfonate ionsAcid ions.
Specific examples of the compound represented by the formula (III) include compounds represented by the following formulas. The compound represented by the following formula is a compound represented by the formula (III), and R 1a 、R 1d 、R 2a 、R 2d 、R 3a 、R 3d 、R 4a And R is 4d is-SPh, R 1b 、R 1c 、R 2b 、R 2c 、R 3b 、R 3c 、R 4b And R is 4c Is a hydrogen atom, M 1 Is a compound of Si.
Figure BDA0004126813250000141
In the above, R A1 And R is A2 Is any one of the groups represented by the following formulas.
Figure BDA0004126813250000142
R A1 And R is A2 is-OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 3 The compounds of the above formula may have an absorption maximum at, for example, 730 to 890nm or 780 to 840 nm. R is R A1 And R is A2 is-OCH 2 CH 2 N + (CH 3 ) 3 I － The compounds of the formula (I) may have an absorption maximum at 730 to 950nm or 770 to 830nm, for example.
Specific examples of the compound represented by the formula (IV) include compounds represented by the following formulas. The compound represented by the following formula is a compound represented by the formula (IV), and R 1a 、R 1d 、R 2a 、R 2d 、R 3a 、R 3d 、R 4a And R is 4d is-SPh, R 1b 、R 1c 、R 2b 、R 2c 、R 3b 、R 3c 、R 4b And R is 4c Is a hydrogen atom, R A1 And R is A2 Is methoxy, M 3 A compound which is P. The above-mentioned compounds can, for example, beHas an absorption maximum at 965 to 1065nm or 980 to 1050 nm.
Figure BDA0004126813250000151
The compound represented by formula (I), formula (II), formula (III) or formula (IV) is a compound that absorbs near infrared rays of a specific wavelength and transmits visible light. In the present specification, near infrared refers to light having a wavelength of 700nm to 3 μm. The compound represented by the formula (I), the formula (II), the formula (III) or the formula (IV) preferably has an absorption maximum at 700nm to 2500nm, more preferably 700nm to 1500nm, still more preferably 700nm to 1300 nm. The compound represented by the formula (I) may have an absorption maximum at 720 to 820nm or 760 to 780nm, for example. The compound represented by the formula (II) may have an absorption maximum at 700 to 760nm or 700 to 720nm, for example. The compound represented by the formula (III) may have an absorption maximum at, for example, 730 to 890nm, 780 to 840nm, 730 to 950nm or 770 to 830 nm. The compound represented by the formula (IV) may have an absorption maximum at 965 to 1065nm or 980 to 1050nm, for example.
The average transmittance of the compound represented by the formula (I), the formula (II), the formula (III) or the formula (IV) at 450nm to 650nm (i.e., visible light) is preferably 98.0% or more, 98.3% or more, 98.5% or more or 99.0% or more, for example. In the present specification, the transmittance was measured at a measurement wavelength of 300 to 1400nm and a measurement interval of 5.0nm using V-770 (ultraviolet visible near infrared spectrophotometer) manufactured by Japanese Specification Co., ltd. The transmittance was measured after the reference measurement was performed using a glass substrate.
From the viewpoint of obtaining a resin composition excellent in heat resistance and visible light transmittance, the colorant (A1) is preferably a compound represented by formula (I) or formula (II).
The content of the colorant (A1) is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, and even more preferably 40 to 100% by mass, based on the total amount of the colorant (a).
The content of the colorant (A1) may be 0.5 to 60 mass%, 0.9 to 60 mass%, 2 to 60 mass%, 4 to 55 mass%, or 6 to 50 mass% of the total solid content of the resin composition. The "total amount of solid components" in the present specification means the total amount of components obtained by removing the solvent from the resin composition. The total amount of the solid components and the content of each component relative to the total amount can be measured by a known analytical method such as liquid chromatography or gas chromatography.
The colorant (a) may further contain a colorant (hereinafter, also referred to as colorant (A2)) different from the colorant (A1). The colorant (A2) may be a dye or a pigment.
Examples of the dye include a compound classified into a substance having a color tone other than pigment in the color index (The Society of Dyers and Colourists publication) and a known dye described in a dyeing guide (color dyeing company). As the dye, a xanthene dye is preferable.
Xanthene dyes are dyes that comprise compounds having a xanthene backbone. As xanthene dyes, for example, c.i. acid red 51, 52, 87, 92, 94, 289 and 388; c.i. acid violet 9, 30 and 102; c.i. basic red 1 (rhodamine 6G), 2, 3, 4, 8, 10, and 11; c.i. basic violet 10 (rhodamine B) and 11; c.i. solvent red 218; c.i. mediator red 27; c.i. active red 36 (rose bengal B); sulforhodamine G; xanthene dyes described in japanese patent laid-open publication No. 2010-32999; xanthene dyes described in japanese patent No. 4492760. The xanthene dye is preferably a xanthene dye dissolved in an organic solvent.
As the xanthene dye, a commercially available xanthene dye such as "Chugai Aminol Fast Pink R-H/C" manufactured by Zhonghua chemical Co., ltd., and "Rhodamin 6G" manufactured by Tiangang chemical Co., ltd., can be used. As the xanthene dye, a xanthene dye synthesized by the method described in japanese patent application laid-open No. 2010-32999 using a commercially available xanthene dye as a starting material may be used.
As other dyes, azo dyes, cyanine dyes, triphenylmethane dyes, thiazole dyes, and the like can be used,
Figure BDA0004126813250000161
Oxazine dyes, phthalocyanine dyes, quinophthalone dyes, anthraquinone dyes Naphthoquinone dye, quinone imine dye, methine dye, azomethine dye, squaric acid +.>
Figure BDA0004126813250000162
Dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitrodyes, and the like. Examples of such dyes include c.i. solvent dyes, c.i. acid dyes, c.i. direct dyes, c.i. disperse dyes, c.i. basic dyes, c.i. reactive dyes, c.i. intermediate dyes, and c.i. vat dyes.
As the c.i. solvent dye, for example, c.i. solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, and 189; c.i. solvent red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, and 247; c.i. solvents orange 2, 7, 11, 15, 26, 56, 77 and 86; c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, and 60; c.i. solvent blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59: 1. 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136 and 139; c.i. solvents green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.
Examples of the c.i. acid dye include c.i. acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, and 251; c.i. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 57, 66, 73, 76, 80, 88, 91, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, and 426; c.i. acid oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, and 173; c.i. acid violet 6B, 7, 15, 16, 17, 19, 21, 23, 24, 25, 34, 38, 49 and 72; c.i. acid blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90: 1. 91, 92, 93: 1. 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1. 335 and 340; c.i. acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50: 1. 58, 63, 65, 80, 104, 105, 106 and 109.
Examples of the c.i. direct dyes include c.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, and 141; c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, and 250; c.i. direct oranges 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, and 107; c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104; c.i. direct blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 243, 244, 245, 246, 247, 248, 259, 250, 251, 252, 256, 257, 259, 260, 268, 274, 293 and 293; and c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.
As c.i. disperse dyes, for example, c.i. disperse yellow 51, 54, and 76; c.i. disperse violet 26 and 27; and c.i. disperse blue 1, 14, 56 and 60.
Examples of the c.i. basic dye include c.i. basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, and 89; c.i. basic violet 2; c.i. basic red 9; c.i. basic green 1.
As c.i. reactive dyes, for example, c.i. reactive yellow 2, 76, and 116; c.i. active orange 16; c.i. reactive red 36.
As the c.i. intermediate dye, for example, c.i. intermediate yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65; c.i. media red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, and 95; c.i. medium oranges 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48; c.i. vehicle violet 1, 1: 1. 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, and 58; c.i. medium blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83 and 84; and c.i. media green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43.
Examples of the c.i. vat dye include c.i. vat green 1.
Examples of the pigment include pigments classified as pigments (pigment) in the color index (The Society of Dyers and Colourists publication).
Examples of the pigment include a green pigment, a yellow pigment, an orange pigment, a red pigment, a blue pigment, and a violet pigment. As green pigments, c.i. pigment green 7, 36 and 58 are cited. As the yellow pigment, c.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, and 214 can be cited. Examples of orange pigments include c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73. As the red pigment, c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265 may be mentioned. Examples of the blue pigment include c.i. pigment blue 15 and 15: 3. 15: 4. 15:6 and 60. As violet pigments, c.i. pigment violet 1, 19, 23, 29, 32, 36 and 38 may be mentioned. 1 pigment or a plurality of pigments may be used for each color, and pigments of a plurality of colors may be combined.
The rosin treatment, the surface treatment using a pigment derivative having an acid group or a basic group introduced thereto, the grafting treatment of the pigment surface by a polymer compound or the like, the atomization treatment by a sulfuric acid atomization method or the like, the washing treatment by an organic solvent, water or the like for removing impurities, the removal treatment by an ion exchange method or the like for ionic impurities, and the like may be carried out as necessary. The particle size of the pigment is preferably substantially uniform.
The pigment may be dispersed by a dispersion treatment with a pigment dispersant to prepare a pigment dispersion liquid in a state of being uniformly dispersed in a pigment dispersant solution. The pigments may be dispersed individually or by mixing a plurality of pigments. When the pigment dispersant is used, the amount thereof is preferably 10 to 200 parts by mass, more preferably 15 to 180 parts by mass, and even more preferably 20 to 160 parts by mass, per 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid in which the pigment is more uniformly dispersed is obtained in the case where 2 or more pigments are used.
When the colorant (a) contains the colorant (A2), the content of the colorant (A2) is preferably 1 to 80% by mass, more preferably 1 to 70% by mass, and still more preferably 1 to 60% by mass, based on the total amount of the colorant (a).
The content of the colorant (a) in the resin composition may be, for example, 0.5 to 70% by mass, 0.9 to 70% by mass, 1 to 70% by mass, 2 to 65% by mass, 5 to 60% by mass, or 7 to 55% by mass, based on the total amount of solid components. When the content of the colorant (a) is within the above range, the desired spectroscopic characteristics can be more easily obtained.
< resin (B) >
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [ K1] to [ K6]:
resin [ K1]: a copolymer having a structural unit derived from at least 1 (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
resin [ K2]: a copolymer having a structural unit derived from (a), a structural unit derived from (b) and a structural unit derived from a monomer (c) copolymerizable with (a) (wherein, unlike (a) and (b), hereinafter sometimes referred to as "(c)";
resin [ K3]: a copolymer having structural units derived from (a) and structural units derived from (c);
Resin [ K4]: a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c);
resin [ K5]: a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c); or alternatively
Resin [ K6]: a copolymer comprising a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding to a carboxylic anhydride, and a structural unit derived from (c). Among them, the resin (B) is preferably a copolymer (i.e., resin K1 or K2) having a structural unit derived from at least 1 selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and more preferably resin K2.
Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid and 1, 4-cyclohexene dicarboxylic acid; 2, 3-dicarboxylic acid methyl-5-norbornene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, and other carboxyl group-containing bicyclic unsaturated compounds; unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene anhydride; unsaturated mono- [ (meth) acryloyloxyalkyl ] esters of dibasic or higher polycarboxylic acids such as mono [ 2- (meth) acryloyloxyethyl ] succinate and mono [ 2- (meth) acryloyloxyethyl ] phthalate; unsaturated acrylates containing hydroxyl and carboxyl groups such as α - (hydroxymethyl) acrylic acid. Among them, acrylic acid, methacrylic acid, and maleic anhydride are preferable as (a) from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.
The cyclic ether structure having 2 to 4 carbon atoms contained in the monomer (b) may be, for example, at least 1 selected from the group consisting of an oxetane ring, an oxetane ring and a tetrahydrofuran ring. (b) Preferably a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group. In the present specification, "(meth) acrylic acid" means at least 1 selected from acrylic acid and methacrylic acid, "(meth) acryl" means at least 1 selected from acryl and methacryl, and "(meth) acrylate" means at least 1 selected from acrylate and methacrylate.
(b) For example, the monomer (b 1) having an oxetanyl group and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(b 1)"), the monomer (b 2) having an oxetanyl group and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(b 2)"), or the monomer (b 3) having a tetrahydrofuranyl group and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(b 3)") may be mentioned.
Examples of the (b 1) include a monomer (b 1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b 1-1)") and a monomer (b 1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b 1-2)").
Examples of the (b 1-1) include glycidyl (meth) acrylate, β -methyl glycidyl (meth) acrylate, β -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α -methyl-o-vinylbenzyl glycidyl ether, α -methyl-m-vinylbenzyl glycidyl ether, α -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, and 2, 6-tris (glycidoxymethyl) styrene.
Examples of the (b 1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, celloxide 2000, (product of Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER A400, (product of Daicel), 3, 4-epoxycyclohexylmethyl (for example, CYCLOMER M100, (product of Daicel), 3, 4-epoxytricyclo (meth) acrylate [ 5.2.1.0) 2,6 ]Decyl ester, 3, 4-epoxytricyclo (meth) acrylate [5.2.1.0 2,6 ]Decyloxy ethyl ester, and the like.
As the monomer having an oxetanyl group and a (meth) acryloyloxy group, preferred is (b 2), and examples of such (b 2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane and 3-ethyl-3-acryloyloxyethyl oxetane.
The monomer (b 3) having a tetrahydrofuranyl group and a (meth) acryloyloxy group is preferable, and examples of such (b 3) include tetrahydrofurfuryl acrylate (for example, viscoat V #150, manufactured by osaka organic chemical industry co., ltd.) and tetrahydrofurfuryl methacrylate.
From the viewpoint of improving reliability such as heat resistance and chemical resistance of the optical filter, (b) is preferably (b 1). Further, from the viewpoint of obtaining a resin composition excellent in storage stability, (b) is more preferably (b 1-2).
Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylateDodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo (meth) acrylate [5.2.1.0 2,6 ]Decane-8-yl ester (which is also known in the art as dicyclopentyl (meth) acrylate ". Additionally, it is sometimes referred to as tricyclodecyl (meth) acrylate"), [5.2.1.0 ] tricyclo (meth) acrylate 2,6 ](meth) acrylic esters such as decen-8-yl ester (which is known as dicyclopentenyl (meth) acrylate "), -dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthalene (meth) acrylate, benzyl (meth) acrylate, and the like as a conventional name;
hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;
bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [2.2.1] hept-2-ene, 5-ethyl bicyclo [2.2.1] hept-2-ene, 5-hydroxy bicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl bicyclo [2.2.1] hept-2-ene, 5- (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxy bicyclo [2.2.1] hept-2-ene, 5-ethoxy bicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxy bicyclo [2.2.1] hept-2-ene, 5, 6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxy bicyclo [ 2.1] hept-2-ene, 5, 6-diethoxy bicyclo [ 2.1] hept-2-ene, 5-diethoxy [ 2.1] hept-2-ene, 5-dihydroxy bicyclo [2.2.1] hept-2-ene, 5, 6-di (hydroxymethyl) bicyclo [ 2.2.1.1 ] hept-2-ene, 5-dihydroxy-2.1 ] bicyclooxy-carbonyl, 5-di (2.1-hydroxy) bicyclo [ 2.1.1.1 ] hept-2-ene;
Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like;
styrene, alpha-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, and the like.
Among them, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hept-2-ene are preferable from the viewpoints of copolymerization reactivity and heat resistance.
In the resin [ K1], the total mole number of all the structural units constituting the resin [ K1] is preferably:
the structural unit derived from (a) is 2 to 60 mol% and
The structural unit derived from (b) is 40 to 98 mol%,
more preferably:
10 to 50 mol% of the structural unit derived from (a), and
the structural unit derived from (b) is 50 to 90 mol%.
When the ratio of each structural unit of the resin [ K1] is within the above range, there is a tendency that the storage stability of the resin composition, the developability when a colored pattern to be described later is formed, and the solvent resistance of the optical filter are excellent.
The resin [ K1] can be produced by, for example, a method described in the literature "Experimental method for polymer synthesis" (release of 1 st printing 1972, 3 months and 1 days, 1 st edition, kagaku Kogyo Co., ltd.) and a cited literature described in the literature.
Specifically, the following method is mentioned: the prescribed amounts of (a) and (b), the polymerization initiator, the solvent, and the like are charged into a reaction vessel, and heated and kept warm while stirring under a nitrogen atmosphere, for example. The polymerization initiator, solvent, and the like used herein are not particularly limited, and those commonly used in the art can be used. For example, as the polymerization initiator, there may be mentioned azo compounds (2, 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile) and the like) or organic peroxides (benzoyl peroxide and the like), and as the solvent, there is no particular limitation as long as it is a solvent that dissolves each monomer, and for example, the solvent (E) described later may be used as the solvent (E) of the resin composition.
In the resin [ K2], the total mole number of all the structural units constituting the resin [ K2] is preferably:
the structural unit from (a) is 2 to 45 mole percent,
2 to 95 mol% of structural units derived from (b), and
the structural unit derived from (c) is 1 to 65 mol%,
more preferably:
the structural unit from (a) is 5 to 40 mole percent,
The structural unit derived from (b) is 5 to 80 mol%, and
the structural unit derived from (c) is 5 to 60 mol%.
When the ratio of each structural unit of the resin [ K2] is within the above range, there is a tendency that the storage stability of the colored resin composition, the developability upon formation of a colored pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained optical filter are excellent.
The resin [ K2] can be produced by the same method as the resin [ K1], except that (a), (b) and (c) can be used instead of (a) and (b), for example.
In the resin [ K3], the total mole number of all the structural units constituting the resin [ K3] is preferably:
the structural unit derived from (a) is 2 to 60 mol% and
the structural unit derived from (c) is 40 to 98 mol%,
more preferably:
10 to 50 mol% of the structural unit derived from (a), and
the structural unit derived from (c) is 50 to 90 mol%.
The resin [ K3] can be produced by the same method as the resin [ K1], except that (a) and (c) are used instead of (a) and (b), for example.
The resin [ K4] can be produced by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms of (b) to a carboxylic acid and/or carboxylic anhydride of (a). First, a copolymer of (a) and (c) was produced by the same method as the resin [ K3 ]. The ratio of the structural unit derived from (a) to the structural unit derived from (c) is preferably the same as that of the resin [ K3 ]. Then, the cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer. Specifically, after the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and the reaction catalyst (e.g., tris (dimethylaminomethyl) phenol, etc.) for (b), carboxylic acid or carboxylic anhydride and cyclic ether, and polymerization inhibitor (e.g., hydroquinone, etc.) are placed in the flask and reacted at 60 to 130℃for 1 to 10 hours, for example, to thereby produce the resin [ K4]. The charging method, the reaction conditions such as the reaction temperature and the reaction time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like.
(b) The amount of (a) to be used is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). When the amount of (b) is in this range, the color resin composition tends to have good storage stability, developability at the time of forming a pattern, and a balance among solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern. The (b) used in the resin [ K4] is preferably (b 1), more preferably (b 1-1), in view of the high reactivity of the cyclic ether and the difficulty of leaving unreacted (b).
The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c).
Resin [ K5] was produced by the same method as resin [ K4] except that (b) was used instead of (a) and (a) was used instead of (b). That is, first, a copolymer of (b) and (c) is obtained, and then, a cyclic ether derived from (b) and a carboxylic acid or carboxylic anhydride derived from (a) which are contained in the copolymer of (b) and (c) are reacted, whereby the resin K5 can be obtained. Wherein the ratio of the structural unit derived from (b) to the structural unit derived from (c) is preferably based on the total mole number of all the structural units constituting the copolymer:
The structural unit derived from (b) is 5 to 95 mol%, and
the structural unit derived from (c) is 5 to 95 mol%,
more preferably:
10 to 90 mol% of the structural unit derived from (b), and
the structural unit derived from (c) is 10 to 90 mol%.
The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). The (b) used in the resin [ K5] is preferably (b 1), more preferably (b 1-1), in view of the high reactivity of the cyclic ether and the difficulty of leaving unreacted (b).
The resin [ K6] is a resin obtained by further reacting a carboxylic anhydride with the resin [ K5 ]. Specifically, the hydroxyl group generated by the reaction of the cyclic ether from (b) with the carboxylic acid or carboxylic anhydride from (a) is reacted with the carboxylic anhydride. Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene anhydride. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1 mole based on 1 mole of the amount of (a).
Specific examples of the resin (B) include 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer and 3, 4-epoxytricyclo acrylate [5.2.1.0 2.6 ]Decyl ester/(meth) acrylic acid copolymer and other resins [ K1 ]]The method comprises the steps of carrying out a first treatment on the surface of the Glycidyl (meth) acrylate/(meth) acrylate benzyl/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene copolymer, benzyl (meth) acrylate/(meth) acrylic acid/acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Resins [ K2 ] such as decyl ester copolymers]The method comprises the steps of carrying out a first treatment on the surface of the Resins [ K3 ] such as benzyl (meth) acrylate/(meth) acrylic acid copolymer and styrene/(meth) acrylic acid copolymer]The method comprises the steps of carrying out a first treatment on the surface of the Resins such as resins obtained by adding benzyl (meth) acrylate/(meth) acrylic acid copolymer to glycidyl (meth) acrylate, resins obtained by adding tricyclodecyl (meth) acrylate/styrene/(meth) acrylic acid copolymer to glycidyl (meth) acrylate, and resins obtained by adding tricyclodecyl (meth) acrylate/(meth) benzyl/(meth) acrylic acid copolymer to glycidyl (meth) acrylate [ K4 ]The method comprises the steps of carrying out a first treatment on the surface of the Resins [ K5 ] such as resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/(meth) glycidyl acrylate with (meth) acrylic acid, resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/styrene/(meth) glycidyl acrylate with (meth) acrylic acid, and the like]The method comprises the steps of carrying out a first treatment on the surface of the Resins such as resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/(meth) glycidyl acrylate with (meth) acrylic acid and further reacting the resultant resin with tetrahydrophthalic anhydride [ K6 ]]Etc.
Resin [ K2 ]]For example benzyl methacrylate/acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ] 2,6 ]Decane-8-yl ester/acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Decane-9-yl ester copolymer. The copolymer has a structural unit represented by the following formula.
Figure BDA0004126813250000271
The resin [ K4] may be, for example, a resin obtained by adding glycidyl methacrylate to a tricyclodecyl methacrylate/benzyl methacrylate/methacrylic acid copolymer.
The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3000 to 100000, more preferably 5000 to 50000, and even more preferably 5000 to 30000. When the molecular weight is within the above range, the hardness of the optical filter tends to be high, the residual film ratio tends to be high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be high.
The dispersity [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.
The acid value of the resin (B) is preferably 50 to 170mg-KOH/g, more preferably 60 to 150mg-KOH/g, still more preferably 70 to 135mg-KOH/g, in terms of solid content conversion. The acid value here means the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B), and can be obtained by, for example, titration using an aqueous potassium hydroxide solution.
The content of the resin (B) may be, for example, 7 to 99 mass%, 53 to 99 mass%, 7 to 65 mass%, 13 to 60 mass%, or 17 to 55 mass% with respect to the total amount of solid components in the resin composition. When the content of the resin (B) is within the above range, a colored pattern can be formed well, and the resolution and the film residue ratio of the colored pattern tend to be improved.
< polymerizable Compound (C) >)
The polymerizable compound (C) is a compound that can be polymerized by a living radical and/or an acid generated by the polymerization initiator (D). The polymerizable compound (C) is, for example, a polymerizable compound having an ethylenically unsaturated bond, and is preferably (meth) acrylate.
The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate (e.g., dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like. Among them, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate is preferable.
The weight average molecular weight of the polymerizable compound (C) is preferably 150 to 2900, more preferably 250 to 1500.
The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass, based on the total amount of solid components in the resin composition. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a colored pattern and the chemical resistance of the optical filter tend to be improved.
< polymerization initiator (D) >)
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating a living radical, an acid, or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator generating active radicals include an alkylbenzene compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound.
The O-acyl oxime compound is a compound having a partial structure represented by the formula (d 1). Hereinafter, the bonding site is represented.
Figure BDA0004126813250000291
Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxacyclopentylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopropane-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopropane-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9-acetoxy-methyl-1-methyl-phenyl ] -3-methyl-3-yl ] propane-imine. Commercial products such as Irgacure OXE01, OXE02 (both of the above are manufactured by BASF) and N-1919 (manufactured by ADEKA) may also be used. Among them, from the viewpoint of obtaining an optical filter of high brightness, the O-acyloxime compound is preferably at least 1 selected from the group consisting of N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, more preferably N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine or N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine.
The alkyl benzene ketone compound is a compound having a partial structure represented by formula (d 2) or a partial structure represented by formula (d 3). In these partial structures, the benzene ring may have a substituent. From the viewpoint of sensitivity, as the alkyl phenone compound, a compound having a partial structure represented by formula (d 2) is preferable.
Figure BDA0004126813250000292
Examples of the compound having a partial structure represented by the formula (d 2) include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] butan-1-one, and the like. Commercial products such as Omnirad (Irgacure) 369, 907 and 379 (all made by IGM Resins B.V. Co.) can be used.
Examples of the compound having a partial structure represented by the formula (d 3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, an oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzil dimethyl ketal, and the like.
Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine.
Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and the like. Commercially available products such as Omnirad 819 (manufactured by IGM Resins B.V. Co.) may also be used.
Examples of the bisimidazole compound include 2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenylbisimidazole and 2,2' -bis (2, 3-dichlorophenyl) -4,4', 5' -tetraphenylbisimidazole (for example, referring to JP-A-6-75372, JP-A-6-75373 and the like), 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese patent application laid-open No. 48-38403, japanese patent application laid-open No. 62-174204, etc.), biimidazole compounds in which the phenyl group at the 4,4', 5' -position is substituted with a carboalkoxy group (for example, refer to Japanese patent application laid-open No. 7-10913, etc.), and the like.
Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, and the like; 10-butyl-2-chloroacridone; benzil; methyl benzoate; titanocene compounds, and the like. These are preferably used in combination with a polymerization initiator (D1) (particularly an amine) to be described later.
Examples of the polymerization initiator for acid production include 4-hydroxyphenyldimethyl sulfonium p-toluene sulfonate, 4-hydroxyphenyldimethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfonium p-toluene sulfonate, and 4-acetoxyphenyl methyl benzylSulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, and diphenyliodo
Figure BDA0004126813250000311
P-toluenesulfonate, diphenyliodo->
Figure BDA0004126813250000313
Hexafluoroantimonate and the like->
Figure BDA0004126813250000312
Salts, nitrobenzyl p-toluenesulfonate, benzoin p-toluenesulfonate and the like.
As the polymerization initiator (D), a polymerization initiator generating a living radical is preferable, a polymerization initiator containing at least 1 selected from the group consisting of an alkyl phenone compound, a triazine compound, an acyl phosphine oxide compound, an O-acyl oxime compound and a biimidazole compound is more preferable, and a polymerization initiator containing an O-acyl oxime compound is further preferable.
The content of the polymerization initiator (D) may be, for example, 0.1 to 30 parts by mass or 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be short, so that the productivity of the optical filter is improved.
< polymerization initiator aid (D1) >)
The resin composition may further contain a polymerization initiator aid (D1). The polymerization initiator aid (D1) is a compound or sensitizer for promoting the polymerization of the polymerizable compound (C) initiated by the polymerization initiator. The polymerization initiator (D1) is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiator aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone (known as Michaelis ' ketone), 4' -bis (diethylamino) benzophenone, and 4,4' -bis (ethylmethylamino) benzophenone, and among them, 4' -bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (manufactured by Baogu chemical industries, ltd.) can be used.
Examples of the alkoxyanthracene compound include 9, 10-dimethoxy anthracene, 2-ethyl-9, 10-dimethoxy anthracene, 9, 10-diethoxy anthracene, 2-ethyl-9, 10-diethoxy anthracene, 9, 10-dibutoxyanthracene, and 2-ethyl-9, 10-dibutoxyanthracene.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.
When the polymerization initiator (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiator (D1) is within this range, a colored pattern can be further formed with high sensitivity, and the productivity of the optical filter tends to be improved.
< solvent (E) >
The solvent (E) is not particularly limited, and solvents generally used in this field can be used. As the solvent (E), for example, examples thereof include an ester solvent (a solvent containing-COO-and not containing-O-in the molecule) an ether solvent (a solvent containing-O-and not-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and-O-in the molecule), a solvent containing-COO-in the molecule, and a solvent containing-COO-in the molecule an ether solvent (a solvent containing-O-and not-COO-in the molecule) ether ester solvents (solvents containing-COO-and-O-in the molecule).
Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone.
Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, and 1, 4-di-n
Figure BDA0004126813250000321
Alkyl, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole, and the like.
Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.
Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.
Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.
Examples of the amide solvent include N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
The solvent is preferably 1 or more selected from the group consisting of an ether solvent, an ether ester solvent and an amide solvent, more preferably contains an ether solvent, an ether ester solvent and an amide solvent, and further preferably contains diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate and N-methylpyrrolidone.
The content of the solvent (E) may be 67 to 95 mass%, 70 to 95 mass%, or 75 to 92 mass%, for example, relative to the total amount of the resin composition. In other words, the solid content of the resin composition may be, for example, 5 to 33 mass%, 5 to 30 mass%, or 8 to 25 mass%. When the content of the solvent (E) is within the above range, flatness at the time of coating becomes good, and thus display characteristics tend to become good.
< leveling agent (F) >)
Examples of the leveling agent (F) include silicone surfactants and fluorine surfactants. These surfactants may have a polymerizable group in a side chain.
As the silicone surfactant, a surfactant having a siloxane bond in the molecule can be mentioned. Specifically, DOWSIL (registered trademark) (original Toray Silicone) DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA and SH8400 (trade name, manufactured by DuPont Toray Specialty Material Co., ltd.); KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (made by singer chemical industries, inc.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (MOMENTIVE PERFORMANCE MATERIALS JAPAN, manufactured by contract corporation) and the like are used as the silicone-based surfactant.
Alternatively, the silicone surfactant may be a silicone surfactant having a fluorine atom. Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC corporation) and the like are exemplified as the silicone-based surfactant.
Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, fluorine (registered trademark) FC430 and FC431 (manufactured by sumitomo 3M corporation) may be mentioned; megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (DIC corporation); eftop (registered trademark) EF301, EF303, EF351, and EF352 (mitsubishi material electronics corporation); surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by AGC corporation, former asahi corporation); e5844 (manufactured by King further laboratory Co., ltd.) and the like as the fluorine-based surfactant.
From the viewpoint of obtaining an optical filter having good flatness, the content of the leveling agent (F) may be, for example, 0.001 to 0.2 mass%, 0.002 to 0.1 mass%, or 0.01 to 0.05 mass% with respect to the total amount of the resin composition. The pigment dispersant is not contained in the above-mentioned content.
< other ingredients >
The resin composition of the present embodiment may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like, as needed.
As described later, the resin composition of the present embodiment may be used for a near infrared cut filter or a near infrared transmission filter.
< method for producing resin composition >
The resin composition of the present embodiment can be prepared, for example, by mixing the colorant (a) and the resin (B), and the polymerizable compound (C), the polymerization initiator (D), the solvent (E), the leveling agent (F), the polymerization initiator auxiliary (D1), and other components, as needed. The resin composition after mixing is preferably filtered by a filter having a pore size of about 0.01 to 10. Mu.m.
< optical Filter and method for manufacturing the same >
An optical filter according to an embodiment of the present invention includes a cured product of the above resin composition. The optical filter may be composed of a cured product of the above resin composition. Since the cured product of the resin composition transmits visible light sufficiently and absorbs a specific wavelength in the near infrared region, the optical filter of the present embodiment can be used as a near infrared cut filter, for example. The cured product of the resin composition can be used as a near infrared ray transmission filter having a specific wavelength for transmitting near infrared rays. Therefore, the optical filter according to the present embodiment can be used for an infrared sensor and a display device (for example, a liquid crystal display device, an organic EL device, or electronic paper).
The cured product of the resin composition can be obtained, for example, by irradiating the resin composition with light or by heating the resin composition.
The optical filter containing the compound represented by the formula (I), the formula (II), the formula (III) or the formula (IV) as the colorant (A) preferably has an absorption maximum at 700nm to 2500nm, more preferably at 700nm to 1500nm, still more preferably at 700nm to 1300 nm. The optical filter containing the compound represented by the formula (I) may have an absorption maximum at 720 to 820nm or 760 to 780nm, for example. The optical filter containing the compound represented by the formula (II) may have an absorption maximum at, for example, 700 to 760nm or 700 to 720 nm. The optical filter containing the compound represented by the formula (III) may have an absorption maximum at, for example, 730 to 890nm, 780 to 840nm, 730 to 950nm, or 770 to 830 nm. The optical filter containing the compound represented by the formula (IV) may have an absorption maximum at 965 to 1065nm or 980 to 1050nm, for example.
The thickness of the optical filter is preferably 20 μm or less, more preferably 6 μm or less, further preferably 3 μm or less, further preferably 1.5 μm or less, particularly preferably 0.5 μm or less. The thickness of the optical filter is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more. The thickness of the optical filter may be, for example, 0.1 to 30 μm, 0.1 to 20 μm or 0.5 to 6 μm.
The method for manufacturing the optical filter is not particularly limited, and it can be manufactured by a conventionally known method. For example, the optical filter may be formed on an arbitrary substrate by photolithography, inkjet method, or printing method. Among them, photolithography is preferable.
Examples of the substrate include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda lime glass coated with silica on the surface, resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, and silicon. Further, a substrate having a thin film of aluminum, silver/copper/palladium alloy, or the like on these substrates may be used. A substrate obtained by performing HMDS treatment on a silicon substrate may be used. Further, a substrate having other optical filters, resin layers, transistors, circuits, and the like over these substrates may be used.
In the photolithography method, first, the above-mentioned resin composition is coated on a substrate, and the resin composition is dried to form a layer of the resin composition. The resin composition may be applied by, for example, a spin coating method, a slit coating method, or a slit/spin coating method. The thickness of the layer of the resin composition may be appropriately determined according to the thickness of the target optical filter. The drying of the resin composition can be performed by, for example, heat drying (prebaking) and/or reduced pressure drying. The temperature of the heat drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. The drying under reduced pressure is preferably carried out at a pressure of 50 to 150Pa and a temperature in the range of 20 to 25 ℃.
Then, the resin composition layer is exposed to light through a photomask having a predetermined pattern, and then developed by contacting it with a developer, thereby forming a colored pattern composed of a cured product of the resin composition. The pattern of the photomask may be appropriately determined according to the use of the optical filter. The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. Such light having a wavelength may be obtained, for example, by cutting light having a specific wavelength range (for example, less than 350 nm) from a predetermined light source with a filter for cutting the wavelength range, or by selectively extracting light having a specific wavelength (for example, around 436nm, around 408nm, or around 365 nm) with a bandpass filter for extracting the wavelength range. The light source may be, for example, a mercury lamp, a light emitting diode, a metal halide lamp or a halogen lamp. In order to uniformly irradiate the entire exposure surface with parallel light and to perform precise alignment of the photomask and the substrate, a reduction projection exposure apparatus or a proximity exposure apparatus using a mask aligner, a stepper, or the like is preferable.
As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable. The concentration of the alkaline compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may contain a surfactant. The development can be performed, for example, by a paddle method, a dipping method, and a spraying method. The substrate may be inclined at an arbitrary angle at the time of development. The unexposed portion of the layer of the resin composition is dissolved in a developer solution by development to be removed.
The resulting colored pattern is preferably post-baked. The post-baking temperature may be, for example, 80 to 250 ℃, 100 to 245 ℃, 150 to 250 ℃ or 160 to 250 ℃. The post-baking time is, for example, 1 to 120 minutes, 2 to 30 minutes or 5 to 60 minutes.
In the photolithography, a cured product of an unpatterned resin composition layer can be obtained without using a photomask and/or without developing during exposure.
Both the cured product and the colored pattern of the resin composition layer are included in the range of the optical filter of the present embodiment.
< solid-state imaging element >
The solid-state imaging device according to one embodiment of the present invention includes the optical filter described above. The optical filter may be a near infrared ray transmission filter and/or a near infrared ray cut filter. The portions other than the optical filter in the solid-state element may be the same as those of the conventionally known solid-state imaging element. Fig. 1 shows an example of a solid-state imaging element.
The solid-state imaging device 100 shown in fig. 1 includes: a semiconductor substrate 2 having a light receiving element or the like (not shown), a near infrared cut filter 4, a near infrared transmission filter 6, a color filter 8, a microlens 10, and a planarizing layer 12. As the near infrared ray cut filter 4 and the near infrared ray transmission filter 6, the above-mentioned optical filters can be used. The color filter 8 is not particularly limited, and conventionally known color filters for forming pixels, such as the color filters described in japanese patent application laid-open publication No. 2014-043556, for example, can be used. The microlens 10 and the planarizing layer 12 are not particularly limited, and known microlenses and planarizing layers can be used.
In the solid-state imaging device 100 shown in fig. 1, the near infrared cut filter 4, the color filter 8, and the microlens 10 are stacked in this order, but the positions of the near infrared cut filter 4 and the color filter 8 may be exchanged. Further, another layer may be further provided between the near infrared cut filter 4 and the color filter 8.
The solid-state imaging element of the present embodiment can be used for an infrared sensor and a display device (for example, a liquid crystal display device, an organic EL device, or electronic paper). That is, according to one embodiment of the present invention, an infrared sensor and a display device including the solid-state imaging element can be provided.
Examples (example)
Synthesis example 1
Synthesis of colorant (A1-1) as a compound represented by formula (II). The colorant (A1-1) was Furuyama, T., shimaki, F., saikawa, N.et al., "One-step synthesis of ball-shaped metal complexes with a main absorption band in the near-IR region", scientific Reports 2019,9,16528, DOI:10.1038/s41598-019-53014-7, and was synthesized by the method described in the above-mentioned publication.
Figure BDA0004126813250000381
Synthesis example 2
Synthesis of colorant (A1-2) as a compound represented by formula (I). The colorant (A1-2) was Furuyama, T., shimaki, F., saikawa, N.et al., "One-step synthesis of ball-shaped metal complexes with a main absorption band in the near-IR region", scientific Reports 2019,9,16528, DOI:10.1038/s41598-019-53014-7, and was synthesized by the method described in the above-mentioned publication.
Figure BDA0004126813250000382
< synthetic example 3>
Synthesis of colorant (A1-3) as a compound represented by formula (IV). The colorant (A1-3) was Nagao Kobayashi, taniyuki Furuyama, and Koh Satoh, "Rationally Designed Phthalocyanines Having Their Main Absorption Band beyond 1000nm", journal of the American Chemical Society,2011 133,49,19642-19645, DOI:10.1021/ja208481q, and was synthesized by the method described in the above paper.
Figure BDA0004126813250000391
< synthetic example 4>
The colorant (A1-4) is synthesized as a compound represented by the formula (III). The colorant (A1-4) was Taniyuki Furuyama, takashi Ishii, naoya Ieda, hajime Maeda, and Masahito Segi, "Cationic axial ligands on sulfur substituted silicon (iv) phtalocyanines: improved hydrophilicity and exceptionally red-shifted absorption into the NIR region", chemical Communications,2019,55,7311-7314, DOI:10.1039/C9CC03022K, and was synthesized by the method described in the above paper.
Figure BDA0004126813250000392
Synthesis example 5
The colorant (A1-5) is synthesized as the compound represented by the formula (III). The colorant (A1-5) was Taniyuki Furuyama, takashi Ishii, naoya Ieda, hajime Maeda, and Masahito Segi, "Cationic axial ligands on sulfur substituted silicon (iv) phtalocyanines: improved hydrophilicity and exceptionally red-shifted absorption into the NIR region", chemical Communications,2019,55,7311-7314, DOI:10.1039/C9CC03022K, and was synthesized by the method described in the above paper.
Figure BDA0004126813250000401
< synthetic example 6>
The colorants (A1-6) are synthesized as the compound represented by the formula (III). The colorant (A1-6) was Taniyuki Furuyama, takashi Ishii, naoya Ieda, hajime Maeda, and Masahito Segi, "Cationic axial ligands on sulfur substituted silicon (iv) phtalocyanines: improved hydrophilicity and exceptionally red-shifted absorption into the NIR region", chemical Communications,2019,55,7311-7314, DOI:10.1039/C9CC03022K, and was synthesized by the method described in the above paper.
Figure BDA0004126813250000411
< synthetic example 7>
Synthetic resin (B-1) as follows. First, a proper amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, the flask was replaced with a nitrogen atmosphere, 340 parts of propylene glycol monomethyl ether acetate was charged, and the flask was heated to 80℃while stirring. Then, the mixture was dropped for 5 hoursAdding 57 parts of acrylic acid and 3, 4-epoxy tricyclo [5.2.1.0 of acrylic acid 2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]54 parts of a mixture of decane-9-yl esters (molar ratio 1:1), 239 parts of benzyl methacrylate and 73 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution of 40 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) in which the polymerization initiator was dissolved in 197 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition of the initiator solution, the mixture was kept at 80℃for 3 hours and then cooled to room temperature, whereby a copolymer (resin (B-1)) solution having a viscosity of 127mPas and a solid content of 37.0% by weight as measured by a B-type viscometer (23 ℃) was obtained. The resulting copolymer had a weight average molecular weight Mw of 9.4X10 3 The dispersion was 1.89, and the acid value in terms of solid content was 114mg-KOH/g. The resin (B-1) has the following structural units.
Figure BDA0004126813250000412
Synthesis example 8
Synthetic resin (B-2) as follows. First, 100 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and an air duct, and the mixture was stirred while nitrogen was replaced, and the temperature was raised to 120 ℃. Then, 1 part by mass of Perbutyl (registered trademark) O (manufactured by japan oil and fat corporation) was added to 100 parts by mass of the monomer mixture, which was composed of 7 parts by mass of tricyclodecyl methacrylate, 27 parts by mass of benzyl methacrylate, and 13 parts by mass of methacrylic acid. This was added dropwise from a dropping funnel to the flask over 2 hours, and stirred at 120℃for 2 hours to obtain a copolymer. Then, the flask was subjected to air substitution, and 7 parts by mass of glycidyl methacrylate, 0.34 part by mass of triphenylphosphine and 0.07 part by mass of methyl hydroquinone were added to the copolymer solution, and the reaction was continued at 120 ℃. After the reaction was completed when the acid value in terms of solid content became 105mg-KOH/g, 32 parts by mass of propylene glycol monomethyl ether acetate was added thereto, whereby a solution of an alkali-developable photosensitive resin (B-2)) (Mw: 30000) having a solid content of 30% was obtained.
Test example 1]
Example 1
[ preparation of resin composition ]
The following components were mixed to obtain a resin composition 1.
Figure BDA0004126813250000421
Examples 2 to 5 and comparative example 1
[ preparation of resin composition ]
Resin compositions 2 to 5 and the resin composition of comparative example 1 were obtained in the same manner as in example 1 except that the colorant (a) of example 1 was changed to the following compound in an equivalent amount (0.015 parts by mass).
Example 2: coloring agent (A1-2)
Example 3: coloring agent (A1-3)
Example 4: coloring agent (A1-4)
Example 5: coloring agent (A1-5)
Comparative example 1:4, 5-octa (2, 5-dichlorophenoxy) -3,6- { tetra (2, 6-dimethylphenoxy) -tetra (benzylamino) } vanadyl phthalocyanine
[ formation of coating film ]
The resin compositions prepared in examples 1 to 5 and comparative example 1 were applied to a 5cm square glass substrate (EAGLE 2000; manufactured by Corning corporation) by spin coating, and then prebaked at 100℃for 3 minutes to obtain a coating film having a thickness of 1.0. Mu.m. The thickness of the coating film was measured using a film thickness measuring apparatus (DEKTAK 3; manufactured by Japanese vacuum technology Co., ltd.).
[ optical Properties ]
The average transmittance of the obtained coating film at 450nm to 650nm is shown in Table 1.
TABLE 1
Average value of transmittance of 450-650 nm
Example 1 99.0
Example 2 98.3
Example 3 98.5
Example 4 98.0
Example 5 98.3
Comparative example 1 98.0
[ Heat resistance ]
Then, the obtained coating film was subjected to a heat resistance test at 120℃for 10 minutes. The transmittance of the coating film before and after the heat resistance test was measured, and the rate of increase in transmittance (i.e., the rate of decrease in absorbance) at the maximum absorption wavelength present in the wavelength range shown in table 2 was calculated. The results are shown in Table 2. The transmittance increase rate is a value obtained by subtracting the transmittance before the heat resistance test from the transmittance after the heat resistance test.
TABLE 2
Wavelength (nm) Rate of increase in transmittance
Example 1 700～720 1.1
Example 2 760～780 0.3
Example 4 780～840 0.6
Example 5 770～830 1.0
Comparative example 1 880～900 1.5
[ light fastness ]
An ultraviolet cut filter (COLORED OPTICAL GLASS L; manufactured by HOYA Co., ltd., cut off light of 380nm or less) was disposed on the coating film obtained by baking at 100℃for 3 minutes. The transmittance of the coating film before and after the light resistance test was measured by performing the light resistance test by irradiating xenon light for 48 hours using a light resistance tester (HOYA CPS +: (manufactured by Toyo Seisakusho Co., ltd.). Table 3 shows the increase rate of the transmittance at the maximum absorption wavelength in the wavelength range shown in table 3. The transmittance increase rate is a value obtained by subtracting the transmittance before the light resistance test from the transmittance after the light resistance test.
TABLE 3
Wavelength (nm) Rate of increase in transmittance
Example 2 760～780 0.7
Comparative example 1 880～900 1.5
< test example 2>
Example 6
[ preparation of resin composition ]
The following components were mixed to obtain a resin composition 6.
Colorant (a): 0.015 part by mass of colorant (A1-1)
Resin (B): resin (B-2) 0.81 parts by mass (in terms of solid content)
Polymerizable compound (C): dipentaerythritol polyacrylate (NK ester A-9550 manufactured by Xinzhongcun chemical industry Co., ltd.) 0.54 parts by mass (solid conversion)
Polymerization initiator (D): 0.14 part by mass of 2-methyl-2-morpholin-1- (4-methylsulfanyl-phenyl) propan-1-one (Omnirad 907, manufactured by IGM Resins B.V. Co., ltd.)
Solvent (E): propylene glycol monomethyl ether acetate 2.0 parts by mass
Solvent (E): 6.5 parts by mass of N-methylpyrrolidone
Example 7, comparative example 2
[ preparation of resin composition ]
Resin compositions 7 and comparative example 2 were obtained in the same manner as in example 6 except that the colorant (a) in example 6 was changed to the following compound in an equivalent amount (0.015 parts by mass).
Example 7: coloring agent (A1-4)
Comparative example 2:4, 5-octa (2, 5-dichlorophenoxy) -3,6- { tetra (2, 6-dimethylphenoxy) -tetra (benzylamino) } vanadyl phthalocyanine
[ formation of coating film ]
The colored resin compositions prepared in example 6 and comparative example 2 were applied to a 5cm square glass substrate (EAGLE 2000; manufactured by Corning corporation) by spin coating, and then baked at 100℃for 3 minutes to obtain a coating film having a thickness of 1.0. Mu.m.
[ Heat resistance ]
Then, the obtained coating film was subjected to a heat resistance test at 120℃for 10 minutes, and the transmittance of the coating film before and after the heat resistance test was measured. Table 4 shows the increase rate of the transmittance at the maximum absorption wavelength in the wavelength range shown in table 4.
TABLE 4
Wavelength (nm) Rate of increase in transmittance
Example 6 700～720 0.02
Example 7 780～840 0.90
Comparative example 2 880～900 2.4
[ light fastness ]
An ultraviolet cut filter (COLORED OPTICAL GLASS L; manufactured by HOYA Co., ltd., cut off light of 380nm or less) was disposed on the coating film obtained by baking at 100℃for 3 minutes. The transmittance of the coating film before and after the light resistance test was measured by performing the light resistance test by irradiating xenon light for 48 hours using a light resistance tester (HOYA CPS +: (manufactured by Toyo Seisakusho Co., ltd.). Table 5 shows the increase rate of the transmittance at the maximum absorption wavelength in the wavelength range shown in table 5.
TABLE 5
Wavelength (nm) Rate of increase in transmittance
Example 6 700～720 4.8
Comparative example 2 880～900 5.5
< test example 3>
Resin compositions similar to those of test examples 1 and 2 were prepared using the colorants (A1-6) as the colorant (a), and coating films were formed. As a result of the heat resistance test and the light resistance test under the same conditions as in test example 1 and test example 2, the transmittance increase rate at the maximum absorption wavelength in the wavelength range of 730 to 950nm was lower than that of the comparative example.
Symbol description
2 … semiconductor substrate, 4 … near infrared cut filter, 6 … near infrared transmission filter, 8 … color filter, 10 … microlens, 100 … solid-state imaging element.

Claims (9)

1. A resin composition comprising a colorant and a resin,
the colorant comprises a compound represented by formula (I), formula (II), formula (III) or formula (IV),
Figure FDA0004126813240000011
in the formula (I) and the formula (II),
R x1 ～R x4 each independently represents a chain hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,
the chain hydrocarbon group containing-CH 2 May be substituted by-O-,
the hydrogen atom contained in the chain hydrocarbon group may be substituted with a halogen atom,
the hydrogen atoms contained in the aryl and heteroaryl groups may each be independently substituted with a halogen atom, -OR 1 、－SR 1 or-NR 2 R 3 ，
R 1 Represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, wherein the chain hydrocarbon group contains-CH 2 Can be substituted by-O-, -NR 2 -or-N + (R 2 R 3 )X － Hydrogen atoms contained in the aryl group and the heteroaryl group may be each independently substituted with a halogen atom or a linear or branched alkoxy group having 1 to 20 carbon atoms,
R 2 And R is 3 Each independently represents a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms, and the-CH contained in the hydrocarbon group 2 May be substituted with-O-, or
R 2 And R is R 3 Are bonded to each other to form a ring,
x represents halogen atom, PF 6 、ClO 4 Or BF 4 ，
R in formula (I) y1 ～R y4 Each independently represents a chain hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,
the chain hydrocarbon group containing-CH 2 May be substituted by-O-,
the hydrogen atom contained in the chain hydrocarbon group may be substituted with a halogen atom,
the hydrogen atoms contained in the aryl and heteroaryl groups may each be independently substituted with a halogen atom, -OR 1 、－SR 1 or-NR 2 R 3 ，
Ring Z in formula (II) 1 And ring Z 2 Each independently represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms or a heteroaromatic ring having 2 to 20 carbon atoms,
the hydrogen atoms contained in the aromatic hydrocarbon ring and the heteroaromatic ring may be substituted with halogen atoms, chain hydrocarbon groups having 1 to 20 carbon atoms, -OR 1 、－SR 1 or-NR 2 R 3 ，
R 1 、R 2 Or R is 3 Where there are plural, they may be the same or different,
M 2 represents a metal atom which is divalent and which is a group of atoms,
Figure FDA0004126813240000021
in the formula (III) and the formula (IV),
R 1a ～R 1d 、R 2a ～R 2d 、R 3a ～R 3d and R is 4a ～R 4d Each independently represents a hydrogen atom, a halogen atom, a chain hydrocarbon group having 1 to 20 carbon atoms, -OR 1 、－SR 1 or-NR 2 R 3 ，R 1a ～R 1d 、R 2a ～R 2d 、R 3a ～R 3d And R is 4a ～R 4d At least one of them represents-SR 1 ，
R 1 Represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, wherein the chain hydrocarbon group contains-CH 2 Can be substituted by-O-, -NR 2 -or-N + (R 2 R 3 )X － Hydrogen atoms contained in the aryl group and the heteroaryl group may be each independently substituted with a halogen atom or a linear or branched alkoxy group having 1 to 20 carbon atoms,
R 2 and R is 3 Each independently represents a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms, and the-CH contained in the hydrocarbon group 2 May be substituted with-O-, or
R 2 And R is R 3 Are bonded to each other to form a ring,
x represents halogen atom, PF 6 、ClO 4 Or BF 4 ，
R A1 And R is A2 Each independently represents-OR 4 ，
R 4 Represents a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, wherein the chain hydrocarbon group contains-CH 2 Can be substituted by-O-, -NR 5 -or-N + (R 5 R 6 )X － －，
R 5 And R is 6 Each independently represents a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms,
R 1 、R 2 、R 3 、R 5 or R is 6 Where there are plural, they may be the same or different,
m in formula (III) 1 Represents a tetravalent metal atom or a nonmetallic atom,
M in formula (IV) 3 Represents a pentavalent metal atom or a non-metal atom,
y in formula (IV) － Representing a monovalent anion.
2. The resin composition according to claim 1, further comprising a polymerizable compound and a polymerization initiator.
3. The resin composition according to claim 1 or 2, wherein the resin is a copolymer comprising structural units derived from at least 1 selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and structural units derived from monomers having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond.
4. The resin composition according to any one of claims 1 to 3, wherein R x1 ～R x4 Each independently represents an aryl group having 6 to 20 carbon atoms,
R y1 ～R y4 each independently represents an aryl group having 6 to 20 carbon atoms,
ring Z 1 And ring Z 2 Each independently represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms,
M 2 represents Ru, fe, cu, zn, co, ni or Pd, which is a group of metals,
R 1a ～R 1d 、R 2a ～R 2d 、R 3a ～R 3d and R is 4a ～R 4d Each independently represents a hydrogen atom or－SR 1 ，
R 4 Represents a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms, and the chain hydrocarbon group contains-CH 2 Can be substituted by-O-, -NR 5 -or-N + (R 5 R 6 )X － －，
M 1 Represents Si and is preferably selected from the group consisting of Si,
M 3 and P.
5. The resin composition according to claim 4, wherein R x1 ～R x4 Each independently represents an aryl group having 6 to 10 carbon atoms,
R y1 ～R y4 each independently represents an aryl group having 6 to 10 carbon atoms,
ring Z 1 And ring Z 2 Each independently represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms,
M 2 the expression "Ru" is used to indicate,
R 1 represents an aryl group having 6 to 10 carbon atoms,
R 4 represents a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms, and the chain hydrocarbon group contains-CH 2 Can be substituted by-O-or-N + (R 5 R 6 )X － －。
6. The resin composition according to claim 5, wherein the colorant comprises a compound represented by formula (I) or formula (II).
7. The resin composition according to any one of claim 1 to 3, wherein the colorant comprises a compound represented by any one of the following formulas,
Figure FDA0004126813240000041
wherein R is A1 And R is A2 Representation of-OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 3 、－OCH 2 CH 2 N + (CH 3 ) 3 I － Or hydroxyl.
8. An optical filter comprising a cured product of the resin composition according to any one of claims 1 to 7.
9. A solid-state imaging device comprising the optical filter according to claim 8.
CN202180063312.5A 2020-09-17 2021-09-10 Resin composition Pending CN116234867A (en)

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